2,4-dichloro-1-hydropyridinium triflate | 1255923-07-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2,4-dichloro-1-hydropyridinium triflate
• 英文别名: 2,4-dichloropyridin-1-ium trifluoromethanesulfonate
• CAS: 1255923-07-9
• 化学式: CHF₃O₃S*C₅H₃Cl₂N
• 分子量: 298.07
• InChiKey: BEAFOMCURDACQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  67.26
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  四(三苯基膦)钯 、 2,4-dichloro-1-hydropyridinium triflate 以 甲苯 为溶剂， 生成 trans-chloro(2-chloro-1,4-dihydro-4-pyridylidene)bis(triphenylphosphine)nickel(II) triflate
  参考文献：
  名称：

  Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

  摘要：

  We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh3)(2)Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and C-13 NMR data indicate the importance of carbenoid mesomeric contributions in their compound class.. The catalytic performance of the palladium complexes trans-(pyridylidene)Pd(PPh3)(2)Cl as precursors in Suzuki-Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh3)(4) are reacted with 2,4-dichloropyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results.

  DOI：

  10.1021/om100431u
• 作为产物：
  描述：

  2,4-二氯吡啶 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 反应 18.0h， 以85.7%的产率得到2,4-dichloro-1-hydropyridinium triflate
  参考文献：
  名称：

  Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

  摘要：

  We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh3)(2)Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and C-13 NMR data indicate the importance of carbenoid mesomeric contributions in their compound class.. The catalytic performance of the palladium complexes trans-(pyridylidene)Pd(PPh3)(2)Cl as precursors in Suzuki-Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh3)(4) are reacted with 2,4-dichloropyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results.

  DOI：

  10.1021/om100431u

文献信息

• Synthesis of Bench-Stable<i>N-</i>Quaternized Ketene<i>N</i>,<i>O</i>-Acetals and Preliminary Evaluation as Reagents in Organic Synthesis
  作者：Danielle L. McConnell、Alisha M. Blades、Danielle Gomes Rodrigues、Phoebe V. Keyes、Justin C. Sonberg、Caitlin E. Anthony、Sofia Rachad、Olivia M. Simone、Caroline F. Sullivan、Jonathan D. Shapiro、Christopher C. Williams、Benjamin C. Schafer、Amy M. Glanzer、Holly L. Hutchinson、Ashley B. Thayaparan、Zoe A. Krevlin、Isabella C. Bote、Yasin A. Haffary、Sambat Bhandari、Jack A. Goodman、Max M. Majireck

  DOI：10.1021/acs.joc.1c01764

  日期：2021.9.17

  catalyst-free electrophilic aromatic substitutions. N-(1-Ethoxyvinyl)-2-halopyridinium salts can be employed in peptide couplings as a derivative of Mukaiyama reagents or react with amines in nucleophilic aromatic substitutions under mild conditions. These preliminary reactions illustrate the broad potential of these currently understudied compounds in organic synthesis.

  N -季铵化乙烯酮N , O -缩醛通常是一类不稳定、瞬态的化合物，最常作为反应中间体观察到。在这份报告中，我们描述的一般合成方法的各种工作台稳定Ñ -quaternized烯酮Ñ，ö -acetals经由治疗与炔属醚和适当的布朗斯台德酸或路易斯酸（三氟甲磺酸，三氟甲，或吡啶或苯胺碱三氟甲磺酸钪（III））。所得吡啶鎓盐和苯胺鎓盐可用作多种反应类型的试剂或合成中间体。例如，N -(1-ethoxyvinyl)pyridinium 或anilinium 盐可以热释放高反应性的O-乙基烯酮离子用于无酸催化剂的亲电芳香取代。N -(1-Ethoxyvinyl)-2-halopyridinium 盐可作为 Mukaiyama 试剂的衍生物用于肽偶联，或在温和条件下与亲核芳族取代中的胺反应。这些初步反应说明了这些目前尚未研究的化合物在有机合成中的广泛潜力。